Organosilicon compound

Silicones and Other Silicon Compounds, Reinhold Publ. Corp., New York, 1949 E. G. Rochow, An Introduction to the Chemistry of the Silicones, John Wiley and Sons, New York, 2nd ed, 1951 A. Hunyar, Chemie der Silikone, Verlag Techrtik, Berlin, 1952 R. R. McGregor, Silikones and Their Uses, McGraw-Hill Publ. Co., London, 1954 C. Eabom, Organosilicon Compounds, Butterworths Scientific Publications, London, 1960. 

Formation of metal-carbon bonds (organometallic compounds) 

Gilman and Dunn269 have considered the relations between the organic compounds of silicon and those of carbon. 

Organosilicon compounds can be prepared by reaction of silicon halides with other organometallic compounds. The first such synthesis (1865) was that by Friedel and Crafts270 who heated silicon tetrachloride with dimethyl-zinc in a sealed tube at 200°  

Stock and Somieski271 much later prepared the methylsilanes CH3SiH3 and (CH3)2SiH2 from mono- and di-chlorosilane, respectively, at room temperature. 

Two other important properties of silicon-carbon bonds are that carbonium ions /3 and carbanions (or metalloid equivalents) a to silicon are favoured over alternatives, i.e. that situations involving Si—C—C+ and Si—C- are thermodynamically relatively good. 

The first of these phenomena is known as the /3-effect (3), and can be represented as follows  

One thing that silicon cannot do with any great success is form multiple bonds compounds with Si=Si or Si=C bonds are quite rare and normally 

Eabom and R. W. Bott, Synthesis and reactions of the silicon-carbon bond, Organo-metallic Compounds of the Group IV Elements, ed. A. G. MacDiarmid, Vol. 1, Part 1. Marcel Dekker, New York (1968). 

Fleming, Some uses of silicon compounds in synthesis. Chem. Soc. Rev. 10,83(1981). 

TL 27 883 (1986) (I2, A1C13 or SnCLf-variable stereochemistry) JOC 52 1100 (1987) (stereochemistry of halogenation) 

R1CH=CBrSiMe3 lCu(SPh)L .. R1CH=CR2Br R1CH=CR2R3 

R1CH=CBrSiMe3 jlCu(SPb)L 5 - R1CH=CR2Br R1CH=CR2R3 

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Figure 4.50 from Molecular Parameters for Organosilicon Compounds Calculated from Ab Initio Computations, Grigoras S and T H Lame, Journal of Computational Chemistry 9 25-39, 1988. Reprinted by permission of John Wiley Sons, Inc. 

Some organosilicon compounds undergo transmetallation. The allylic cyanide 461 was prepared by the reaction of an allylic carbonate with trimethylsi-lyl cyanide[298]. The oriho esters and acetals of the o. d-unsaturated carbonyl compounds 462 undergo cyanation with trimefhylsilyl cyanide[95]. 

Our discussion to this point has been limited to molecules m which the chirality center IS carbon Atoms other than carbon may also be chirality centers Silicon like carbon has a tetrahedral arrangement of bonds when it bears four substituents A large number of organosilicon compounds m which silicon bears four different groups have been resolved into their enantiomers... 

V. Bazant, V. Choalovsky, and J. Rathousky, Organosilicon Compounds, Vol. 1, Chemistry of Organosilicon Compounds, Academic Press, Inc., New York, 1965. 

C. Eabom, Organosilicon Compounds, Buttersworth Scientific PubUcations, Lander, U.K., 1960. 

V. M. Mikhaylov and V. N. Penskh, Production of Monomer and Polymer Organosilicon Compounds, English transL, No. AD-779129, NTIS, U.S. Dept, of Commerce, Springfield, Va., p. 18. 

H. W. Post, Silicones and Other Organosilicon Compounds, Reinhold, New York, 1949. 

The possibility of the existence of organosilicone compounds was first predicted by Dumas in 1840, and in 1857 Buff and Wohler found the substance now known to be trichlorosilane by passing hydrochloric acid gas over a heated mixture of silicone and carbon. In 1863 Friedel and Crafts prepared tetraethylsilane by reacting zinc diethyl with silicon tetrachloride. 

Fluorinated organosilicon compounds may be prepared from readUy available fluorohalocarbons by using phosphorous amides [84, 85, 86] or tetrakis(dimeth-ylamino)ethylene [57] for the generation of the fluoroorganic nucleophiles (equations 61-69). 

Reactions of cyclic acetals with organosilicon compounds 97MI42. 

V. Bazant, V. Chvalovsky and J. Rathousky. Organosilicon Compounds, Vols 1 and 2, Academic Press. New York and London. 1965 V. Bazant et al., Handbook of Organosilicon Compounds, Vols 1-4. Marcel Dekker. New York. 1973 V. Chvalovsky and J. Rathousky, Organosilicon Compounds, Vols 5 and 6. Institute of Chemical Process Fundamentals of the Czechoslovak Academy of Sciences, Prague, 1977. 

D. R. M. Walton, Organosilicon compounds. Dictionary of Organometallic Compounds. Vol. 2 and Supplements 1-4, Chapman and Hall, London, 1984. 

A. G. Brook and A. R. Bassindale. Molecular rearrangements of organosilicon compounds. Rearrangements in Ground and Excited States, ed. P. de Mayo. Vol. 2. Academic Press. New York (1980). 

P. F, Hudrlik, Organosilicon compounds in organic synthesis, J. Organometal. Chem. Library 1, 127 (1976). 

Hiyama, T. Organosilicon Compounds in Cross-Coupling Reactions. In Metal Catalyzed Cross-Coupling Reactions, Diederich, F., Stang, P. J., Eds. Wiley-VCH Weinhein, 1998 Chapter 10. 

V. Bazant et al., Handbook of Organosilicon Compounds, Marcel Dekker Inc., New York 1975. 

Eaborn, C. Organosilicon Compounds, Butterworths Sci. Publ., London 1960... 

Peroxy Compounds of Transition Metals J. A. Connor and E. A. V. Ebsworth The Direct Synthesis of Organosilicon Compounds J. J. Zuckerman... 

Hirsch A, Vostrowsky O (2001) Dendrimers with Carbon Rich-Cores. 217 51-93 Hiyama T, Shirakawa E (2002) Organosilicon Compounds. 219 61-85 Holmberg K, see Hager M (2003) 227 53-74... 

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